JP7601873B2 - Adhesion release coating - Google Patents

Description

The present invention relates to a fouling release coating composition, a method for preparing such a fouling release coating, and a marine structure coated with such a fouling release coating.

Surfaces submerged in seawater are prone to the fouling of marine organisms such as green and brown algae, slime molds, barnacles, mussels and tubeworms. In marine structures such as vessels (e.g. ships, tankers), oil platforms and buoys, such fouling is undesirable and has economic consequences. Fouling can lead to biological deterioration of the surface, increased loading and accelerated corrosion. In ships, fouling increases frictional resistance, which causes a decrease in speed and/or increased fuel consumption. It can also reduce maneuverability.

Anti-fouling paints are used to prevent the settlement and growth of marine organisms. Traditionally, two types of anti-fouling paints have been used: self-polishing anti-fouling paints and fouling-removing anti-fouling paints.

Self-polishing antifouling paints contain an antifouling agent and a binder that gradually dissolves and/or hydrolyzes in seawater, allowing the seawater to erode the coating surface, thereby exposing a new surface. The most successful self-polishing antifouling paints are based on hydrolyzable binders, such as (meth)acrylate binders with hydrolyzable silyl esters. The gradual hydrolysis in seawater results in the controlled release of the antifouling agent from the coating.

Fouling release antifouling paints work by providing a coating with low surface tension and low modulus of elasticity, providing a fouling release surface to which marine organisms do not adhere or which are easily washed away by rubbing water against the surface or washing. Such coatings are often based on polysiloxane-based binders. The fouling release surface created by polysiloxane binders is effective in preventing large foulants from permanently adhering to the surface. However, polysiloxane surfaces have not shown good resistance to soft foulants such as slime mold and algae over time.

Polysiloxane-based fouling release coatings (FRCs) have traditionally been used without biocides. However, as mentioned above, a challenge with FRCs is the adhesion of soft foulings such as slime molds and algae. The use of polyether-modified silicone oils in FRCs is known to reduce the adhesion of slime molds and algae. Furthermore, in recent years, biocides effective against slime molds and algae have been added to FRCs to further improve fouling prevention. One type of biocide that has been found to work well is a pyrithione salt, such as copper pyrithione. However, FRCs containing biocides have room for improvement, especially with regard to fouling prevention, long-term performance, and adhesion.

The addition of biocides has been shown to provide many technical advantages, including fouling prevention, reduced spray dust, and improved storage stability and enhanced fouling prevention coatings. Specifically, FRCs containing polyether modified polysiloxane oils have been complemented by the addition of antifoulants (e.g., pyrithione salts such as zinc pyrithione (ZnPt) and copper pyrithione (CuPt)). Antifoulants (e.g., CuPt) are typically present at about 5-7% dry weight, and polyether modified silicone oils are typically present at about 1-5% dry weight. However, the addition of solid antifoulants adversely affects the viscosity of the coating (increases viscosity). The increase in viscosity can usually be compensated for by increasing the concentration of the solvent (thinning) to maintain good application properties, but this results in an increase in VOCs and associated adverse health effects for the applicator and environmental effects. The present invention discloses a method to compensate for the increased viscosity without increasing the solvent content (VOC) of the coating formulation, and in some cases, even reducing the VOC of the original composition.

The inventors have surprisingly found that by incorporating relatively large amounts of non-ionic hydrophilic modified silicone oils having specific parameters (molecular weight and HLB), it is possible to obtain antifouling agent-containing deposit release formulations having low VOC, good application properties (viscosity), good film uniformity and improved antifouling properties.

It has been believed that one cannot have a large amount of polyether modified silicone oil in a polysiloxane-based fouling release coating because it results in too much water uptake in the film, poor film uniformity, and high polarity resulting in poor adhesion. US Pat. No. 5,399,433 teaches a coating having an optimum concentration of 4-7 wt. % polyether modified silicone oil in combination with a copper pyrithione biocide. US Pat. No. 5,499,433 teaches a coating containing 0.13 wt. % polyether modified silicone oil in combination with a copper pyrithione biocide. US Pat. No. 5,499,433 also discusses that a large amount of polyether modified silicone oil (more than 10 wt. %) gives poor adhesion. US Pat. No. 5,499,433 discloses a coating composition containing 4 wt. % polyether modified silicone oil.

US Patent No. 5,399, 667 discloses higher amounts of silicone oil, but for a different binder system based on metal bridged organopolysiloxane-thioblock vinyl copolymer. US Patent No. 5,399, 667 discloses an antifouling composition, with a comparative example having a polyether modified silicone oil, but with a high HLB value (14.5) and present in a large amount (more than 30% by weight on a dry basis). The inventors have shown in their examples that such a large amount and high HLB value results in poor results in the deposit release coating.

International Publication No. WO 2011/076856 International Publication No. 2014/077205 International Publication No. 2017/009297 European Patent No. 2514776 European Patent No. 2103655

In one aspect, the present invention comprises:
a) a curable polysiloxane-based binder comprising at least 50% by weight of polysiloxane moieties;
b) a stain repellent;
c) 10 to 30% by dry weight,
i) a hydrophilic-lipophilic balance (HLB) of 1 to 12, and
ii) Mn between 500 and 18,000 g/mol
and a non-ionic hydrophilically modified polysiloxane having the formula:

Viewed from another aspect, the present invention comprises:
a) a curable polysiloxane-based binder comprising at least 50% by weight of polysiloxane moieties;
b) a stain repellent;
c) 10 to 30% by dry weight,
i) a hydrophilic-lipophilic balance (HLB) of 1 to 12, and
ii) Mw between 1,000 and 50,000 g/mol
and a non-ionic hydrophilically modified polysiloxane having the formula:

Viewed from another aspect, the present invention comprises:
a) a curable polysiloxane-based binder comprising at least 50% by weight of polysiloxane moieties;
b) a stain repellent;
c) 10 to 30% by dry weight,
i) a relative weight of the hydrophilic portion in the range of 5 to 60% by weight, and
ii) Mn between 500 and 18,000 g/mol
and a non-ionic hydrophilically modified polysiloxane having the formula:

Viewed from another aspect, the present invention comprises:
a) a curable polysiloxane-based binder comprising at least 50% by weight of polysiloxane moieties;
b) a stain repellent;
c) 10 to 30% by dry weight,
i) a relative weight of the hydrophilic portion in the range of 5 to 60% by weight, and
ii) Mw between 1,000 and 50,000 g/mol
and a non-ionic hydrophilic polysiloxane having the formula:

Viewed from another aspect, the present invention provides a marine structure comprising, on at least a portion of its exterior surface, a fouling release coating as defined herein.

Viewed from another aspect, the present invention provides a method for preparing an adhesion release coating composition as defined herein, comprising the steps of:
a) a curable polysiloxane-based binder comprising at least 50% by weight of polysiloxane moieties;
b) a stain repellent;
c) 10 to 30% by dry weight,
i) HLB from 1 to 12, and
ii) Mn of 500 to 18,000 g/mol and/or Mw of 1,000 to 50,000 g/mol
and a non-ionic hydrophilic modified polysiloxane having the formula:
Typically, a method is provided that includes the step of mixing in at least one solvent.

Viewed from another aspect, the present invention provides a method for preparing an adhesion release coating composition as defined herein, comprising the steps of:
a) a curable polysiloxane-based binder comprising at least 50% by weight of polysiloxane moieties;
b) a stain repellent;
c) 10 to 30% by dry weight,
i) the relative weight of the hydrophilic portion in the range of 5 to 60% by weight, and
ii) Mn of 500 to 18,000 g/mol and/or Mw of 1,000 to 50,000 g/mol
and a non-ionic hydrophilic modified polysiloxane having the formula:
Typically, a method is provided that includes the step of mixing in at least one solvent.

Viewed from another aspect, the present invention provides a kit for preparing an adhesion release coating composition as defined herein, comprising:
(i) a first container containing a curable polysiloxane-based binder, a stain repellent, and/or a non-ionic hydrophilically modified polysiloxane;
(ii) a second container containing a crosslinker and/or curing agent, and optionally a catalyst;
(iii) optionally, a third vessel containing a catalyst;
(iv) Optionally, instructions for combining the contents of the containers.

DEFINITIONS As used herein, the term "fouling release composition" or "fouling release coating composition" refers to a composition that, when applied to a surface, provides a fouling release surface to which marine organisms have difficulty permanently attaching.

As used herein, the term "binder" refers to the film-forming components of the composition. The polysiloxane-based binder of the composition is the primary binder in the composition, i.e., forms at least 50% by weight of the binder present. As used herein, the term "binder" does not include added oils. Added oils are not considered film-forming components herein.

As used herein, the term "paint" refers to a composition that includes a deposit release coating composition as described herein and, optionally, a ready-to-use solvent, such as a solvent for spraying. Thus, the deposit release coating composition may be a coating itself, or the deposit release coating composition may be a concentrate to which a solvent is added to produce a coating.

As used herein, the term "polysiloxane" refers to a polymer containing siloxane, i.e., -Si-O- repeating units.

As used herein, the term "polysiloxane-based binder" refers to a binder that contains at least 50% by weight, preferably at least 60% by weight, and more preferably at least 70% by weight, of repeat units containing the motif -Si-O-, based on the total weight of the polymer. The polysiloxane-based binder may contain up to 99.99% by weight, based on the total weight of the polymer, of repeat units containing the motif -Si-O-. The repeat units -Si-O- may be linked in a single sequence or may be interrupted by non-siloxane moieties, e.g., organic-based moieties.

As used herein, the term "non-degradable polysiloxane-based binder" refers to a polysiloxane-based binder that does not undergo hydrolysis or erosion in seawater.

As used herein, the term "alkyl" refers to a saturated, linear, branched, or cyclic group. An alkyl group can be substituted or unsubstituted.

As used herein, the term "cycloalkyl" refers to a cyclic alkyl group.

As used herein, the term "alkylene" refers to a divalent alkyl group.

As used herein, the term "alkenyl" refers to an unsaturated, linear, branched, or cyclic group. Alkenyl groups can be substituted or unsubstituted.

As used herein, the term "aryl" refers to a group that contains at least one aromatic ring. The term aryl encompasses heteroaryl as well as fused ring systems in which one or more aromatic rings are fused to a cycloalkyl ring. An aryl group can be substituted or unsubstituted. An example of an aryl group is phenyl, i.e. _{, C6H5} . A phenyl group can be substituted or unsubstituted.

As used herein, the term "substituted" refers to a group in which one or more, e.g., up to six, more specifically 1, 2, 3, 4, 5 or 6, of the hydrogen atoms in the group are independently replaced with the corresponding number of listed substituents. As used herein, the term "optionally substituted" means substituted or unsubstituted.

As used herein, the term "arylalkyl" group refers to a group in which the bond to Si is through the alkyl moiety.

As used herein, the term "polyether" refers to a compound containing two or more -O- bonds interrupted by alkylene units.

As used herein, the terms "poly(alkylene oxide)", "poly(oxyalkylene)" and "poly(alkylene glycol)" refer to compounds that contain repeating units of -alkylene-O-. Typically, the alkylene is ethylene or propylene.

As used herein, the term "(meth)acrylate" encompasses both methacrylate and acrylate.

As used herein, the term weight percent is based on the dry weight of the coating composition, unless otherwise specified.

As used herein, the term "PDI" or polydispersity index refers to the ratio Mw/Mn, where Mw refers to the weight average molecular weight and Mn refers to the number average molecular weight. PDI is sometimes also referred to as D (dispersity).

As used herein, the term "volatile organic compounds (VOCs)" refers to compounds that have a boiling point below 250°C.

As used herein, "antifouling agent" refers to a biologically active compound or mixture of biologically active compounds that prevents the settlement of marine organisms on a surface and/or prevents the growth of marine organisms on a surface and/or promotes the detachment of marine organisms from a surface.

The present invention relates to
a) a curable polysiloxane-based binder comprising at least 50% by weight of polysiloxane moieties;
b) a stain repellent;
c) 10 to 30% by dry weight,
i) a hydrophilic-lipophilic balance (HLB) of 1 to 12, and
ii) Mn of 500 to 18,000 g/mol and/or Mw of 1,000 to 50,000 g/mol
and a non-ionic hydrophilically modified polysiloxane having the formula:

Polysiloxane-based binder The binder in the adhesion release coating composition comprises a curable polysiloxane-based binder component (a). The polysiloxane-based binder is preferably a non-degradable curable polysiloxane-based binder. When the polysiloxane is a non-degradable polysiloxane-based binder, the adhesion release coating composition of the present invention provides a pure adhesion release coating.

The polysiloxane-based binder present in the coating composition of the present invention comprises at least 50% by weight of polysiloxane moieties, preferably greater than 60% by weight of polysiloxane moieties, and even more preferably greater than 70% by weight of polysiloxane moieties, such as 99.99% by weight or more of polysiloxane moieties. Typical ranges include 50-100% by weight of polysiloxane moieties, 60-99.999% by weight of polysiloxane moieties, or 70-99.99% by weight of polysiloxane moieties in the polysiloxane-based binder.

The polysiloxane moiety is defined as a repeating unit containing the motif -Si-O-, based on the total weight of the polysiloxane binder. The weight percent of the polysiloxane moiety can be determined based on the stoichiometric weight ratio of the starting materials in the polysiloxane synthesis. Alternatively, the polysiloxane content can be determined using analytical techniques such as IR or NMR.

Typically, the weight percent of the polysiloxane portion is calculated based on the molar ratio of the reactive starting materials in the polysiloxane synthesis. If a molar excess of monomer is present in the reaction mixture, such molar excess is not counted. Only monomer that is capable of reacting based on the stoichiometry of the reaction is taken into account.

Information regarding the weight percent polysiloxane content in commercially available polysiloxane-based binders is readily available from suppliers.

It should be understood that the polysiloxane-based binder may consist of a single repeating sequence of siloxane units or may be interrupted by non-siloxane moieties, e.g., organic moieties. Preferably, the polysiloxane-based binder contains only Si-O repeat units.

The organic moieties may include, for example, alkylene, arylene, poly(alkylene oxide), amide, thioether, or combinations thereof, and preferably, the organic moieties may include, for example, alkylene, arylene, poly(alkylene oxide), amide, or combinations thereof. In certain embodiments, the polysiloxane-based binder does not include thio groups.

The polysiloxane-based binder present in the inventive release coating composition can in principle be any curable polysiloxane-based binder. By curable, it is meant that the polysiloxane-based binder contains functional groups that allow crosslinking reactions to occur between the polysiloxane-based binder molecules or via a crosslinking agent.

The polysiloxane-based binder is preferably an organopolysiloxane having terminal and/or pendant curing reactive functional groups. A minimum of two curing reactive functional groups per molecule is preferred. Examples of curing reactive functional groups are silanol, alkoxy, acetoxy, enoxy, ketoxime, alcohol, amine, epoxy and/or isocyanate. Preferred polysiloxane-based binders include curing reactive functional groups selected from silanol, alkoxy or acetoxy groups. The curing reaction is typically a condensation curing reaction. The polysiloxane-based binder may optionally include more than one type of curing reactive group and be cured, for example, by both condensation curing and amine/epoxy curing.

The polysiloxane-based binder may consist of only one type of polysiloxane, or it may be a mixture of different polysiloxanes.

A preferred polysiloxane binder present in the adhesion release coating composition of the present invention is represented by the following formula (D1):

In the formula,
each ^R1 is independently selected from a hydroxyl group, a _C1-6 -alkoxy group, a _C1-6 -hydroxyl group, a _C1-6 -epoxy-containing group, a _C1-6 amine group, or O-Si( ^R5 ) _3-z ( ^R6 ) _z ;
each ^R2 is independently selected from _C1-10 alkyl, _C6-10 aryl, _C7-10 alkylaryl, or _C1-6 alkyl substituted with poly(alkylene oxide) and/or groups described as ^R1 ;
each ^R3 and ^R4 is independently selected from _C1-10 alkyl, _C6-10 aryl, _C7-10 alkylaryl, or _C1-6 alkyl substituted with poly(alkylene oxide);
each ^R5 is independently a hydrolyzable group such as a _C1-6 alkoxy group, an acetoxy group, an enoxy group, or a ketoxy group;
each ^R6 is independently selected from an unsubstituted _C1-6 alkyl group or a substituted _C1-6 alkyl group;
z is 0 or an integer from 1 to 2;
x is an integer equal to or greater than 2,
y is an integer of 2 or greater.

Preferably, R ¹ is selected from a hydroxyl group and O—Si(R ⁵ ) _3-z (R ⁶ ) _z , where R ⁵ is a C _1-6 alkoxy group, R ⁶ is a _{C 1-6 alkyl} , and z is 0 or an integer from 1 to 2. More preferably, R ¹ is selected from a hydroxyl group and O—Si(R ⁵ ) _3-z (R ⁶ ) _z , where R ⁵ is a C _1-3 alkoxy group, R ⁶ is a _{C 1-3 alkyl} , and z is 0 or an integer from 1 to 2. Even more preferably, R ¹ is a hydroxyl group.

Preferably, ^R2 is a _C1-10 alkyl group. More preferably, ^R2 is a _C1-4 alkyl group, even more preferably a _C1-2 alkyl group, and even more preferably a methyl group. Preferably, each ^R2 is the same.

Preferably, R ³ is a C _1-10 alkyl group. More preferably, R ³ is a C _1-4 alkyl group, even more preferably a C _1-2 alkyl group, and even more preferably a methyl group. Preferably, each R ³ is the same.

Preferably, ^R4 is a _C1-10 alkyl group. More preferably, ^R4 is a _C1-4 alkyl group, even more preferably a _C1-2 alkyl group, and even more preferably a methyl group. Preferably, each ^R4 is the same.

More preferably, R ¹ is a hydroxyl group, and R ² , R ³ and R ⁴ are each a methyl group.
The preferred polysiloxane binder present in the adhesion release coating composition of the present invention is represented by the formula (D2) below.

In the formula,
each ^R1 is independently selected from a hydroxyl group, a _C1-6 -alkoxy group, a _C1-6 -hydroxyl group, a _C1-6 -epoxy-containing group, a _C1-6 amine group, or O-Si( ^R5 ) _3-z ( ^R6 ) _z ;
Each of ^R2 to ^R4 is methyl;
each ^R5 is independently a hydrolyzable group such as a _C1-6 alkoxy group, an acetoxy group, an enoxy group, or a ketoxy group;
each ^R6 is independently selected from an unsubstituted _C1-6 alkyl group or a substituted _C1-6 alkyl group;
z is 0 or an integer from 1 to 2;
x is an integer equal to or greater than 2,
y is an integer of 2 or greater.

Another preferred polysiloxane binder present in the adhesion release coating composition of the present invention is represented by the following formula (D3):

where R ¹ , R ² , R ³ , R ⁴ and x and y are as defined for (D1), R ^x is a C _2-3 alkyl, each L1 is 0 to 50 and each L2 is 0 to 50, provided that L1+L2 is 2 to 50, preferably 4 to 40, more preferably 4 to 20, most preferably 4 to 10, and L3 is 1 to 200, preferably 2 to 100, most preferably 5 to 50. The polysiloxane moiety must form a minimum of 50% by weight of the molecule.

The polysiloxane binder of the present invention is preferably represented by formula D1.

Those skilled in the art will recognize that polysiloxane-based binders may contain small amounts of impurities, such as cyclic siloxanes, such as D4, D5, and D6 cyclic siloxanes, which are residues of polysiloxane synthesis, where the (D4, D5, or D6) designation refers to the number of repeating Si-O units in the cyclic polysiloxane (i.e., 4, 5, or 6 repeating Si-O units in the cyclic polysiloxane). For health, safety, and environmental reasons, it is preferable to limit the amount of cyclic polysiloxanes present in the coating. In a preferred embodiment, the polysiloxane-based binder contains less than 5%, preferably less than 2%, and more preferably less than 1% cyclic polysiloxanes. In a particularly preferred embodiment, the polysiloxane-based binder is free of cyclic polysiloxanes.

The weight average molecular weight of the polysiloxane binder present in the adhesion release coating composition of the present invention is preferably 400 to 150,000 g/mol, more preferably 1000 to 120,000 g/mol, and even more preferably 5000 to 110,000 g/mol.

In one embodiment, the polysiloxane binder (a) does not meet the HLB parameters of the nonionic hydrophilically modified polysiloxane component (c). Specifically, the polysiloxane binder may have an HLB value of less than 0.5, e.g., less than 0.1.

Preferred coating compositions of the present invention contain 30-95 wt.% polysiloxane-based binder, more preferably 40-90 wt.% polysiloxane-based binder, and even more preferably 50-90 wt.% polysiloxane-based binder, based on the total dry weight of the composition.

Polysiloxane binders suitable for use in the coating compositions of the present invention are commercially available. Representative commercially available non-degradable polysiloxane binders include Xiameter® OHX-0135, Xiameter® OHX-4000, Xiameter® OHX-4010, Xiameter® OHX-4040, Xiameter® OHX-4050, and Xiameter® OHX-4060 from Dow Corning, and PolymerOH 0.08, PolymerOH 0.75, PolymerOH 1, PolymerOH 2, PolymerOH 3.5, PolymerOH 5, PolymerOH 20, and PolymerOH 1.0 from Evonik. 80, and Gelest's DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S42, and DMS-S51.

Antifouling Agent The antifouling coating composition of the present invention comprises an antifouling agent (b).

The terms antifouling agent, biologically active compound, antifouling agent, biocide, toxicant are used in the industry to describe known compounds that act to prevent marine fouling on surfaces. The antifouling agent present in the compositions of the present invention is preferably a marine antifouling agent. The antifouling agent may be inorganic, organometallic or organic. Preferably, the antifouling agent is an organometallic antifouling agent. Suitable antifouling agents are commercially available.

Examples of inorganic antifouling agents include copper and copper compounds such as copper oxide, e.g., cuprous oxide and cupric oxide, copper alloys, e.g., copper-nickel alloys, copper salts, e.g., copper thiocyanate and copper sulfide.

Examples of organometallic antifouling agents include zinc pyrithione; organocopper compounds such as copper pyrithione, copper acetate, copper naphthenate, copper oxine, copper nonylphenolsulfonate, copper bis(ethylenediamine)bis(dodecylbenzenesulfonate) and copper bis(pentachlorophenolate); dithiocarbamate compounds such as zinc bis(dimethyldithiocarbamate) [ziram], zinc ethylenebis(dithiocarbamate) [zineb], manganese ethylenebis(dithiocarbamate) [maneb], and manganese ethylenebis(dithiocarbamate) complexed with a zinc salt [mancozeb].

Examples of organic antifouling agents include heterocyclic compounds such as 2-(tert-butylamino)-4-(cyclopropylamino)-6-(methylthio)-1,3,5-triazine [sibutrin], 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], encapsulated 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], 1,2-benzisothiazolin-3-one, 2-(thiocyanatomethylthio)-1,3-benzothiazole [benthiazole], and 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine; urea derivatives such as 3-(3,4-dichlorophenyl)-1,1-dimethylurea [diuron]; amides and imides of carboxylic acids, sulfonic acids, and sulfenic acids such as N-(dichlorofluroxane)-1,1-dimethylurea [diuron]. N-(2,4,6-trichlorophenyl)phthalimide, N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfamide [dichlohlanide], N-dichlorofluoromethylthio-N',N'-dimethyl-N-p-tolylsulfamide [tolylfluanid], and N-(2,4,6-trichlorophenyl)maleimide; other organic compounds such as pyridinetriphenylborane [TPBP], aminetriphenylborane, 3-iodo-2-propynyl N-butylcarbamate [iodocarb], 2,4,5,6-tetrachloroisophthalonitrile, p-((diiodomethyl)sulfonyl)toluene, and 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile [tralopyril] and quaternary ammonium salts.

Other examples of antifouling agents include tetraalkylphosphonium halides, guanidine derivatives, imidazole-containing compounds such as 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole [medetomidine] and its derivatives, avermectins and its derivatives such as ivermectin, spinosyns and its derivatives such as spinosad, macrocyclic lactones including capsaicin and its derivatives such as phenylcapsaicin, and enzymes such as oxidases, proteolytically, hemicellulolytically, cellulolytically, lipolytically and aminolytically active enzymes.

Preferred antifouling agents are zinc pyrithione, copper pyrithione, zinc ethylene bis(dithiocarbamate) [zineb], 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT] and encapsulated 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT]. Particularly preferred antifouling agents are zinc pyrithione and copper pyrithione, especially copper pyrithione.

In the present invention, FRCs containing non-ionic hydrophilic modified polysiloxane oils have typically been complemented by the addition of pyrithione salt biocides (zinc pyrithione (ZnPt) and copper pyrithione (CuPt)). In the patent literature, CuPt is generally present at about 5-7% dry weight, and polyether modified oils are generally present at about 1-5% dry weight. However, the addition of solid pyrithione salts with acicular morphology adversely affects the viscosity of the coating (increases viscosity). The increase in viscosity can usually be compensated for by increasing the concentration of the solvent (thinning) to maintain good application properties, but with an increase in VOC and the associated adverse health effects and environmental effects. The present invention discloses a method to compensate for the increased viscosity without increasing the solvent content (VOC) of the coating formulation, and in some cases, even reducing the VOC of the original composition.

The biocide is typically present at 1-20% by dry weight of the total coating composition, preferably 1-15%, 2-15% or 3-12% by dry weight of the total coating composition. The use of these antifouling agents is known in antifouling coatings and their use is well known to those skilled in the art. The antifouling agent may be encapsulated or adsorbed onto an inert carrier or bound to other materials for controlled release. These percentages refer to the amount of active antifouling agent present and therefore not the amount of carrier used.

Nonionic hydrophilically modified polysiloxane The coating composition of the present invention comprises a nonionic hydrophilically modified polysiloxane (c). It is understood that this component is different from the polysiloxane binder component (a). That is, the coating composition must comprise two different components (a) and (c). In one embodiment, the polysiloxane binder (a) does not meet the HLB parameters of the nonionic hydrophilically modified polysiloxane component (c). Specifically, the polysiloxane binder may have an HLB value of less than 0.5, for example, less than 0.1.

It is to be understood that the non-ionic hydrophilically modified polysiloxane does not contain reactive groups that react with the binder or crosslinker during the curing reaction at the appropriate curing temperature (0-40°C). Thus, the non-ionic hydrophilically modified polysiloxane is intended to be non-reactive in the curing reaction, particularly with respect to the binder component.

It should be understood that depending on the curing reactive groups on the binder, the hydrophilically modified polysiloxane is selected so that it does not contain groups that, if present during the curing reaction, will react with the binder or the crosslinker. Thus, the non-ionic hydrophilically modified polysiloxane is a non-curable component in the coating composition. As used herein, non-curable means that the non-ionic hydrophilically modified polysiloxane does not react with the binder or the crosslinker during the curing reaction in the temperature range of 0-40°C.

In a preferred embodiment, the non-ionic hydrophilically modified polysiloxane does not contain silicone reactive groups such as Si-OH groups, Si-OR (alkoxy), enoxy, ketoximulup, etc. that may react with the binder or crosslinker (if present) at the appropriate curing temperature (0-40°C).

In certain embodiments, the non-ionic hydrophilically modified polysiloxane does not contain Si-OH or Si-OR (alkoxy, i.e., R=alkyl) groups.

Nonionic hydrophilically modified polysiloxanes are widely used as surfactants and emulsifiers because they contain both hydrophilic and lipophilic groups in the same molecule. The nonionic hydrophilically modified polysiloxane according to the present invention is a polysiloxane that has been modified with nonionic hydrophilic groups to become more hydrophilic compared to the corresponding unsubstituted polysiloxane having the same number of polysiloxane units. Hydrophilicity can be obtained by modification with nonionic hydrophilic groups such as ethers (e.g., polyoxyalkylene groups such as polyethylene glycol and polypropylene glycol), alcohols (e.g., poly(glycerol), amides (e.g., pyrrolidone, polyvinylpyrrolidone, (meth)acrylamide), acids (e.g., carboxylic acids, poly(meth)acrylic acid), amines (e.g., polyvinylamine, (meth)acrylic polymers containing amine groups). Typically, the nonionic hydrophilically modified polysiloxane is an oil.

"Nonionic" in this specification means that the hydrophilically modified polysiloxane does not contain salt moieties, and in particular, typically does not contain metal cations.

The hydrophilicity of the non-ionic hydrophilically modified polysiloxane is determined according to the HLB (hydrophilic-lipophilic balance) parameter. The non-ionic hydrophilically modified polysiloxane of the present invention has an HLB (hydrophilic-lipophilic balance) in the range of 1 to 12, preferably 1.0 to 10, more preferably 1.0 to 8.0, and most preferably 2.0 to 7.0. In a particular embodiment, the non-ionic hydrophilically modified polysiloxane has an HLB in the range of 3.0 to 6.0.

HLB is typically determined herein according to Griffin's model using the formula "wt% of hydrophilic groups"/5 (reference: Griffin, W.C. Calculation of HLB values of non-ionic surfactants, J. Soc. Cosmet. Chem. 1954, 5, 249-256). Thus, in certain embodiments, HLB is calculated according to the formula HLB = "wt% of hydrophilic groups"/5. The HLB parameter is an established parameter for non-ionic surfactants and is readily available from commercial suppliers of non-ionic hydrophilically modified polysiloxanes. The higher the HLB value of a surfactant, the more hydrophilic it is. By wt% of hydrophilic groups is meant the wt% of hydrophilic groups in the non-ionic hydrophilically modified polysiloxane. The wt% of hydrophilic groups can be converted to HLB values and vice versa. HLB values of 1 to 12 correspond, for example, to wt% of hydrophilic groups of 5 to 60 wt%.

The function of non-ionic hydrophilically modified polysiloxanes is to promote the dissolution and migration of biocides to the surface of the coating film. It is also well known that the formation of a hydration layer at the coating-water interface is important for antifouling performance.

If the hydrophilicity of the non-ionic hydrophilic modified polysiloxane is too high, for example due to a high amount of hydrophilic groups in the molecule, this can lead to premature depletion of the biocide and the non-ionic hydrophilic modified polysiloxane due to too high a leaching rate. High hydrophilicity can also lead to poor compatibility with the polysiloxane-based binder matrix, resulting in poor film uniformity and poor adhesion, especially when high oil amounts (>10 wt%) are used.

Methods for controlling the leaching rate of the biocide and non-ionic hydrophilic modified polysiloxane include the molecular weight of the non-ionic hydrophilic modified polysiloxane, its hydrophilicity and its miscibility with the binder. Very low molecular weight non-ionic hydrophilic modified polysiloxanes tend to allow high leaching rates, but too high a molecular weight may not allow the biocide and non-ionic hydrophilic modified polysiloxane to leach at the desired rate.

Thus, in a preferred embodiment, the non-ionic hydrophilically modified polysiloxane has a number average molecular weight (Mn) in the range of 500 to 18,000 g/mol, for example in the range of 1000 to 16,000 g/mol, in particular in the range of 2000 to 15,050 g/mol or 4000 to 15,050 g/mol. Further suitable Mn ranges of the non-ionic hydrophilically modified polysiloxane include 500 to 15,000 g/mol, 1,000 to 13,000 g/mol, or 3,000 to 10,000 g/mol. The number average molecular weight (Mn) values referred to herein correspond to experimentally obtained values, for example obtained by GPC measured against polystyrene standards. This method is described in the experimental section below.

In a preferred embodiment, the non-ionic hydrophilically modified polysiloxane has a weight average molecular weight (Mw) in the range of 1,000 to 50,000 g/mol, preferably 2,000 to 45,000 g/mol, 3,000 to 42,000 g/mol, 4,000 to 40,000 g/mol, or 5,000 to 40,000 g/mol. Further suitable ranges include 5,000 to 30,000 g/mol, for example 5,000 to 25,000 g/mol, or 10,000 to 20,000 g/mol. The weight average molecular weight (Mw) values referred to herein correspond to values experimentally obtained, for example by GPC, measured against polystyrene standards. This method is described in the experimental section below.

The specific range of Mn or Mw is important for the beneficial properties of the present invention. In fact, these molecular weights affect the viscosity, which affects the ease of application and the surface roughness. These molecular weights also affect the migration of the biocide and non-ionic hydrophilic modified polysiloxane to the surface of the coating film, which affects the anti-fouling performance.
It is also preferred that the non-ionic hydrophilically modified polysiloxane has a viscosity in the range of 20 to 4,000 mPa-s, for example in the range of 30 to 3,000 mPa-s, especially in the range of 50 to 2,500 mPa-s, as measured according to the method set out in the experimental section.

The amount of non-ionic hydrophilically modified polysiloxane in the coating composition is also an important parameter. Too little will result in a coating composition with high viscosity, which may result in poor application properties. Alternatively, more solvent will need to be added, resulting in a coating composition with a higher VOC. Too little non-ionic hydrophilically modified polysiloxane may also result in poor long-term fouling protection of the coating, as the non-ionic hydrophilically modified polysiloxane may be depleted from the film too quickly. Too much non-ionic hydrophilically modified polysiloxane will result in poor film uniformity and poor fouling protection.

The nonionic hydrophilically modified polysiloxane is included in the coating composition in an amount of 10-30% by dry weight (e.g., 10-25% by dry weight), preferably 11-29% by dry weight, preferably 12-28% by dry weight, preferably 13-27% by dry weight, preferably 14-26% by dry weight, e.g., 15-25% by dry weight. When two or more different types of nonionic hydrophilically modified polysiloxane are present, these amounts refer to the sum of the nonionic hydrophilically modified polysiloxane components.

Of particular interest are non-ionic hydrophilically modified polysiloxanes in which the relative weight of the hydrophilic moieties (e.g. polyether groups) is 5% or more (e.g. 5-60%) of the total weight, for example 6% or more (e.g. 6-50%), especially 10% or more (e.g. 10-40%) of the total weight of the non-ionic hydrophilically modified polysiloxane. Other suitable ranges for the relative weight of the hydrophilic moieties in the non-ionic hydrophilically modified polysiloxane include 5-60% by weight, preferably 5-50% by weight, more preferably 5-40% by weight, most preferably 10-35% by weight, especially 15-30% by weight.

The weight percent of hydrophilic moieties can be calculated based on the stoichiometric ratios of starting materials in the synthesis of the nonionic hydrophilically modified polysiloxane, or can be determined using analytical techniques such as IR or NMR.

If there is a molar excess of reactants, such molar excess is not taken into account when determining the weight percent of hydrophilic moieties. Only monomers that are able to react based on the stoichiometry of the reaction are taken into account.

If the HLB is known, the weight percent of hydrophilic moieties can also be calculated according to Griffin's model using the formula HLB = "weight percent of hydrophilic groups" / 5.

The non-ionic hydrophilically modified polysiloxanes may contain small amounts of impurities, e.g., cyclic siloxanes such as D4, D5 and D6 cyclic siloxanes, which are residues of polysiloxane synthesis, where the (D4, D5 and D6) designations refer to the number of repeating Si-O units in the cyclic polysiloxane (i.e., 4, 5 or 6 repeating Si-O units in the cyclic polysiloxane). For health, safety and environmental reasons, it is preferred to limit the amount of cyclic polysiloxanes present in the coating composition. In a preferred embodiment, the non-ionic hydrophilically modified polysiloxane contains less than 5%, preferably less than 2%, more preferably less than 1% cyclic polysiloxanes. In a particularly preferred embodiment, the non-ionic hydrophilically modified polysiloxane is free of cyclic polysiloxanes.

In a preferred embodiment, the non-ionic hydrophilically modified polysiloxane is a polyether modified polysiloxane, in other words, the hydrophilic portion is a polyether group.

Preferably, the polyether group comprises at least 3 repeat units, such as at least 5 repeat units. In many interesting embodiments, the oligomer or polymer comprises 5 to 100 repeat units, such as 5 to 50, or 8 to 50, or 8 to 20 repeat units.

In some preferred embodiments, the polyether group (i.e., the oligomeric or polymeric group) has a number average molecular weight (n) in the range of 100 to 2500 g/mol, for example in the range of 200 to 2000 g/mol, particularly in the range of 300 to 2000 g/mol, or in the range of 400 to 1000 g/mol.

Of particular interest are polyether modified polysiloxanes in which the relative weight of the polyether moiety is 5% or more (e.g. 5-60%) of the total weight, for example 6% or more (e.g. 6-50%), especially 10% or more (e.g. 10-40%) of the total weight of the polyether modified polysiloxane.

In one variation of the present invention, the polyether-modified polysiloxane is a polysiloxane to which poly(oxyalkylene) chains have been grafted. An illustrative example of the structure of such a polyether-modified polysiloxane is formula (A):

wherein each R ⁷ is independently selected from C _1-5 -alkyl (including linear or branched hydrocarbon groups) and aryl (e.g., phenyl (—C ₆ H ₅ )), in particular methyl;
each ^R8 is independently selected from -H, _C1-4 -alkyl (e.g., _{-CH3 , -CH2CH3} , _-CH2CH2CH3 , _{-CH (CH3)2, -CH2CH2CH2CH3), phenyl (-C6H5), and C1-4 - alkylcarbonyl ( e.g. , -C} (=O) _CH3 , _{-C (} =O _{) CH2CH3} and -C( ₌ O) _CH2CH2CH3 ), in particular -H _, methyl, and -C(=O) _{CH3 ;}
each R ⁹ is independently selected from C _2-5 -alkylene (e.g., —CH ₂ CH ₂ —, —CH ₂ CH( _{CH 3} ), —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH 2 CH ₂ CH ₂ —, —CH ₂ CH(CH ₂ CH ₃ )—), arylene (e.g., 1,4-phenylene) and C _2-5 -alkylene substituted with aryl (e.g., 1-phenylethylene), especially —CH ₂ CH ₂ — and —CH ₂ CH(CH ₃ )— _;
k is 0 to 240, l is 1 to 60, and k+l is 1 to 240;
n is 0 to 50, m is 0 to 50, and m+n is 1 to 50.

In particular, ^R7 is methyl;
each ^R8 is independently selected _from -H or _C1-4 -alkyl or -C(=O)CH3;
each ^R9 is _-CH2CH2- , _{or -CH2CH2CH2- ,} or _-CH2CH ( _CH3 )- _;
k is 0 to 240, l is 1 to 60, and k+l is 1 to 240;
n is 0 to 50, m is 0 to 50, and m+n is 1 to 50.

It is preferred that all ^R7 groups are the same.

Examples of commercially available polyether-modified polysiloxanes of this type are KF352A, KF353, KF945, KF6012, and KF6017 manufactured by ShinEtsu, and XIAMETER OFX-5220, DOWSIL OFX-5247, XIAMETER OFX-5329, and XIAMETER OFX-5330 manufactured by DOW.

In another variation of the present invention, the polyether-modified polysiloxane is a polysiloxane having poly(oxyalkylene) chains incorporated into its backbone. An illustrative example of the structure of such a hydrophilically modified polysiloxane is formula (B):

wherein each R ⁷ is independently selected from C _1-5 -alkyl (including linear or branched hydrocarbon groups) and aryl (e.g., phenyl (—C ₆ H ₅ )), in particular methyl;
each ^R8 is independently selected from -H, _C1-4 -alkyl (e.g., _{-CH3 , -CH2CH3} , _{-CH2CH2CH -} CH( _CH3 ) ₂ , _{-CH2CH2CH2CH3} ), phenyl ( _-C6H5 ), and _C1-4 -alkylcarbonyl (e.g., -C(= _O ) _CH3 , C(= _O ) _CH2CH3 and -C(=O) _{CH2CH2CH3 )} , in _particular -H _{, methyl} , and -C(=O) _{CH3 ;}
each R ⁹ is independently selected from C _2-5 -alkylene (e.g., —CH ₂ CH ₂ —, —CH ₂ CH( _{CH 3} ), —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH 2 CH ₂ CH ₂ —, —CH ₂ CH(CH ₂ CH ₃ )—), arylene (e.g., 1,4-phenylene) and C _2-5 -alkylene substituted with aryl (e.g., 1-phenylethylene), especially —CH ₂ CH ₂ — and —CH ₂ CH(CH ₃ )— _;
k is 0 to 240,
n is 0 to 50, m is 0 to 50, and m+n is 1 to 50.

In particular, in which ^R7 is methyl,
each ^R8 is independently selected _from -H or _C1-4 -alkyl or -C(=O)CH3;
each ^R9 is _-CH2CH2- , _{-CH2CH ( CH3 )} -, or _{-CH2CH2CH2- ;}
k is 0 to 240,
n is 0 to 50, m is 0 to 50, and m+n is 1 to 50.
It is preferred that all ^R7 groups are the same.

Commercially available hydrophilically modified polysiloxanes of this type are DOWSIL 2-8692 and XIAMETER OFX-3667 manufactured by DOW.

In yet another variation, the polyether-modified polysiloxane is a polysiloxane having polyoxyalkylene chains incorporated into its backbone and grafted to it. An illustrative example of the structure of such a hydrophilically modified polysiloxane is formula (C):

wherein each R ⁷ is independently selected from C _1-5 -alkyl (including linear or branched hydrocarbon groups) and aryl (e.g., phenyl (—C ₆ H ₅ )), in particular methyl;
each ^R8 is independently selected from -H, _C1-4 -alkyl (e.g., _{-CH3 , -CH2CH3} , _-CH2CH2CH3 , _{-CH (CH3)2, -CH2CH2CH2CH3), phenyl (-C6H5), and C1-4 - alkylcarbonyl ( e.g. , -C} (=O) _CH3 , _{-C (} = _O ) _CH2CH3 and -C( ₌ O) _CH2CH2CH3 ), in particular -H _, methyl, and -C(=O) _{CH3 ;}
each R ⁹ is independently selected from C _2-5 -alkylene (e.g., —CH ₂ CH ₂ —, —CH ₂ CH( _{CH 3} )—, —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH 2 CH ₂ CH ₂ —, —CH ₂ CH(CH ₂ CH ₃ )—), arylene (e.g., 1,4-phenylene) and C _2-5 -alkylene substituted with aryl (e.g., ₁ -phenylethylene), especially —CH ₂ CH ₂ — and —CH ₂ CH(CH ₃ )—;
k is 0 to 240, l is 1 to 60, and k+l is 1 to 240;
n is 0 to 50, m is 0 to 50, and m+n is 1 to 50.

In particular, in which ^R7 is methyl,

each ^R8 is -H or _C1-4 -alkyl or -C(=O) _CH3 ;
each ^R9 is _{-CH2CH2- , -CH2CH2CH2-} , or _-CH2CH ( _CH3 ) _{- ;}
k is 0 to 240, y is 1 to 60, and x+y is 1 to 240;
n is 0 to 50, m is 0 to 50, and m+n is 1 to 50.

In the above structures (A), (B) and (C), the groups _-CH2CH ( _CH3 )-, _-CH2CH ( _CH2CH3 )-, etc. can be present in either of two possible orientations. Similarly, it should be understood that the k-fold and l-fold occurring segments are typically randomly distributed in the _polysiloxane structure.

In these embodiments and variations, the polyether or poly(oxyalkylene) is preferably selected from polyoxyethylene, polyoxypropylene, and poly(oxyethylene-co-oxypropylene), sometimes referred to as polyethylene glycol, polypropylene glycol, and poly(ethylene glycol-co-propylene glycol). Thus, in structures (A), (B), and (C) above, each R ⁹ linking the two oxygen atoms is preferably selected from -CH ₂ CH ₂ - and -CH ₂ CH(CH ₃ )-, while each R ⁹ linking the silicon atom and the oxygen atom is preferably selected from C _2-5 -alkyl.

In some embodiments of structures (A), (B) and (C) above, R ⁸ is preferably not hydrogen.

It should be understood that the one or more polyether-modified polysiloxanes may be of different types, for example two or more of the types described above.

In another preferred embodiment, the non-ionic hydrophilically modified polysiloxane contains polyglycerol groups or pyrrolidone groups.

Crosslinking and/or curing agents As previously explained, the polysiloxane-based binder of the present invention is curable and comprises a curing reactive functional group such as a silanol group, a carbinol group, a carboxyl group, an ester group, a hydride group, an alkenyl group, a vinyl ether group, an allyl ether group, an alkoxysilane group, a ketoxime group, an amine group, an epoxy group, an isocyanate group and/or an alkoxy group. Preferably, the polysiloxane-based binder comprises at least two curing reactive functional groups. Optionally, the polysiloxane-based binder comprises two or more types of curing reactive functional groups. Preferably, the polysiloxane-based binder comprises a single type of curing reactive functional group. The appropriate crosslinking and/or curing agent is selected according to the curing reactive functional groups present in the polysiloxane-based binder.

In preferred polysiloxane-based binders, the curing reactive functional groups are silanols, carbinols, alkoxysilanes, isocyanates, amines and/or epoxies. In more preferred polysiloxane-based binders, the curing reactive functional groups are silanols, carbinols and/or alkoxysilanes.

It may be necessary to add a crosslinking agent to obtain the desired crosslink density. When the curing reactive functional group is a silanol, the preferred crosslinking agent is an organosilicon compound represented by the general formula shown below, its partial hydrolysis condensate, or a mixture of the two.

_Rd -Si-K4 _-d
In the formula,
each R is independently selected from an unsubstituted or substituted monovalent hydrocarbon group having from 1 to 6 carbon atoms, a C _1-6 alkyl substituted with a poly(alkylene oxide), or a polysiloxane of the structure (O-(CR ^D ₂ ) _r' ) _r1' - (O-(CR ^D ₂ ) _s' ) _s1' - (Si(R ^PP ) ₂ -O) _t' -Si(R ^PP ) ₃ where r', r1', s' and s1' are integers from 0 to 10, each R ^D is independently selected from H or C _1-4 alkyl, each R ^PP is independently selected from C _1-10 alkyl, C _6-10 aryl, C _7-10 alkylaryl, t' is an integer from 1 to 50, each K is independently selected from a hydrolyzable group such as an alkoxy group, and d is 0, 1 or 2, more preferably 0 or 1.

Preferred crosslinkers of this type include tetraethoxysilane, vinyltris(methylethyloximo)silane, methyltris(methylethyloximo)silane, vinyltrimethoxysilane, methyltrimethoxysilane and vinyltriisopropenoxysilane and their hydrolysis condensation products.

When the curing reactive functional groups are di- or trialkoxy, a separate crosslinker is generally not required.

The crosslinker is preferably present in an amount of 0-10% by weight of the total dry weight of the coating composition. Suitable crosslinkers are commercially available, such as Silcate TES-40 WN from Wacker and Dynasylan A from Evonik.

When the curing reactive functional group is a carbinol, the preferred curing agents are monomeric isocyanates, polymeric isocyanates and isocyanate prepolymers. Polyisocyanates are preferred over monomeric isocyanates due to their lower toxicity. Polyisocyanates can be based, for example, on diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) chemistry. These are supplied, for example, by Covestro under the trade name Desmodur and by Vencorex under the trade name Tolonate. Examples of polyisocyanates are Desmodur N3300, Desmodur 3390 BA/SN, Desmodur N3400, Desmodur N3600, Desmodur N75, Desmodur XP2580, Desmodur Z4470, Desmodur XP2565 and Desmodur VL supplied by Covestro.

Polyisocyanates can be made with different NCO functionalities. NCO functionality is the amount of NCO groups per molecule of polyisocyanate or per molecule of isocyanate prepolymer. Polyisocyanate curing agents with different NCO functionalities can be used.

The curing agent is preferably present in an amount of 0.8 to 2.5 equivalents of NCO groups relative to the amount of hydroxyl groups, preferably 0.9 to 2.0 equivalents, more preferably 0.95 to 1.7 equivalents, and even more preferably 1 to 1.5 equivalents.

If the curing reactive functional group is amine, epoxy or isocyanate, the curing agent is preferably amine, sulfur or epoxy functional.

The curing agent may be, for example, a dual curing agent containing both an amine/sulfur/epoxy/isocyanate and an alkoxysilane. A preferred dual curing agent is represented by the general formula:

In the formula,
LL is independently selected from unsubstituted or substituted monovalent hydrocarbon groups having 1 to 6 carbon atoms;
Each M is independently selected from hydrolyzable groups, such as alkoxy groups;
a is 0, 1 or 2, preferably 0 or 1;
b is an integer from 1 to 6;
Fn is an amine group, an epoxy group, a glycidyl ether group, an isocyanate group or a sulfur group.

Preferred examples of such dual curing agents include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, (3-glycidoxypropyl)trimethoxysilane, 3-mercaptopropyltrimethoxysilane. One particularly preferred curing agent is 3-aminopropyltriethoxysilane, such as Dynasylan AMEO manufactured by Evonik.

This type of dual curing agent can be used as a separate curing agent or can be used to end-capping the polysiloxane binder so that the end groups of the polysiloxane binder are modified prior to the curing reaction. For example, mixing of the polysiloxane binder with the curing agent can be done immediately prior to application of the coating to the article, for example, one hour or more prior to coating, or the polysiloxane binder can be provided in a curable form but left dry to prevent premature curing. In some compositions, the curing agent/end-capping agent is preferably provided separately to the remainder of the coating composition to prevent the coating from curing before it is applied to the object. Thus, the coating composition of the present invention can be provided as a multi-part (preferably three-part) formulation, which is discussed in more detail below.

Catalyst To aid in the curing process, the coating composition of the present invention preferably includes a catalyst. Representative examples of catalysts that can be used include transition metal compounds, metal salts and organometallic complexes of various metals, such as tin, iron, lead, barium, cobalt, zinc, antimony, cadmium, manganese, chromium, nickel, aluminum, gallium, germanium, titanium, boron, lithium, potassium, bismuth and zirconium. The salts are preferably salts and/or chelates of long-chain carboxylic acids or organometallic salts.

Examples of suitable tin-based catalysts include, for example, dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin diacetate, dibutyltin 2-ethylhexanoate, dibutyltin dineodecanoate, dibutyltin dimethoxide, dibutyltin dibenzoate, dibutyltin acetoacetonate, dibutyltin acetylacetonate, dibutyltin alkylacetoacetonate, dioctyltin dilaurate, dioctyltin dioctoate, dioctyltin diacetate, dioctyltin 2-ethylhexanoate, dioctyltin dimethoxide, dioctyl ... Examples of commercially available tin catalysts include tin tin dimethylsulfate, tin tin dimethoxide, tin dibenzoate, tin tin acetoacetonate, tin tin acetylacetonate, tin tin alkylacetoacetonate, tin dibutyrate, tin bisneodecanoate, tin dineodecanoate, tin naphthenate, tin butyrate, tin oleate, tin caprylate, tin octanoate, tin stearate, tin triethyl tartrate, isobutyltin trichlorate, and tin octanoate. Examples of commercially available tin catalysts include BNT-CAT 400 and BNT-CAT 500 from BNT Chemicals, FASCAT 4202 from PMC Organometallix, and Metatin Katalysator 702 from DOW. Preferred tin catalysts are dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin diacetate, and dioctyltin dilaurate.

Examples of suitable zinc catalysts are zinc 2-ethylhexanoate, zinc naphthenate and zinc stearate. Examples of commercially available zinc catalysts include K-KAT XK-672 and K-KAT670 manufactured by King Industries, and Borchi Kat22 manufactured by Borchers.

Examples of suitable bismuth catalysts are organobismuth compounds such as bismuth 2-ethylhexanoate, bismuth octanoate, and bismuth neodecanoate. Examples of commercially available organobismuth catalysts are Borchi Kat 24 and Borchi Kat 315 from Borchers, K-KAT XK-651 from King Industries, Reaxis C739E50 from Reaxis, and TIB KAT716 from TIB Chemicals.

Examples of suitable titanium catalysts are organotitanium catalysts such as titanium naphthenate, tetrabutyl titanate, tetrakis(2-ethylhexyl)titanate, triethanolamine titanate, tetra(isopropenyloxy)titanate, titanium tetrabutanolate, titanium tetrapropanolate, titanium tetraisopropanolate and chelated titanates such as diisopropyl bis(acetylacetonyl)titanate, diisopropyl bis(ethylacetoacetonyl)titanate and diisopropoxytitanium bis(ethylacetoacetate). Examples of suitable commercially available titanium catalysts are Tyzor IBAY from Dorf Ketal and TIB KAT 517 from TIB Chemicals.

Other suitable catalysts are iron catalysts such as iron stearate and iron 2-ethylhexanoate, lead catalysts such as lead octoate and lead 2-ethyloctoate, cobalt catalysts such as cobalt-2-ethylhexanoate and cobalt naphthenate, manganese catalysts such as manganese 2-ethylhexanoate, and zirconium catalysts such as zirconium naphthenate, tetrabutyl zirconate, tetrakis(2-ethylhexyl)zirconate, triethanolamine zirconate, tetra(isopropenyloxy)-zirconate, zirconium tetrabutanolate, zirconium tetrapropanolate, and zirconium tetraisopropanolate.

An even more suitable catalyst is a zirconate ester.

The catalyst may also be an organic compound such as triethylamine, guanidine, amidine, cyclic amines, tetramethylethylenediamine, 1,4-ethylenepiperazine, and pentamethyldiethylenetriamine. Further examples include aminosilanes, such as 3-aminopropyltriethoxysilane and N,N-dibutylaminomethyl-triethoxysilane.

In a preferred embodiment, the catalyst is a tin, bismuth and/or zinc catalyst, more preferably a tin and/or bismuth catalyst.

Preferably, the catalyst is present in the coating composition of the present invention in an amount of 0.01 to 5 wt.%, more preferably 0.05 to 4 wt.%, based on the total dry weight of the coating composition.

Additive Oil The coating composition of the present invention optionally comprises an additive oil. Preferably, the coating composition of the present invention comprises 0 to 30 wt. %, more preferably 0.1 to 15 wt. %, of additive oil, based on the solids content of the coating composition. The non-ionic hydrophilically modified polysiloxanes described herein are not considered "additive oils." Thus, the additive oil is a different oil than the non-ionic hydrophilically modified polysiloxanes described herein.

Suitable non-reactive additive oils are silicone oils such as methylphenyl silicone oil, petroleum oils, polyolefin oils, polyaromatic oils, fluororesins such as polytetrafluoroethylene or fluid fluorinated alkyl or alkoxy-containing polymers, or lanolin and lanolin derivatives, and other sterols and/or sterol derivatives as disclosed in WO2013024106, or combinations thereof. A preferred non-reactive additive oil is methylphenyl silicone oil.

A further additive oil optionally present in the coating composition of the present invention is a fluorinated amphiphilic polymer/oligomer as described in WO2014131695.

The coating compositions of the present invention optionally include a hydrophilically modified additive oil. The hydrophilically modified additive oil may be a hydrophilically modified sterol and/or sterol derivative as described in WO2016004961, or a hydrophilically modified acrylic polymer as described in WO2019101920 and WO2019101912.

Non-reactive hydrophilic modified additive oils are typically modified by the addition of non-ionic monomeric, oligomeric or polymeric groups that may be polar and/or capable of hydrogen bonding to enhance interactions with polar solvents, especially water, or with other polar oligomeric or polymeric groups. Examples of these groups include amides (e.g., pyrrolidone, poly(vinylpyrrolidone), poly[N-(2-hydroxypropyl)methacrylamide]), poly(N,N-dimethacrylamide), acids (e.g., poly(acrylic acid)), alcohols (e.g., poly(glycerol), polyHEMA, polysaccharides, poly(vinyl alcohol)), ketones (polyketones), aldehydes (e.g., poly(aldehyde guluronate), amines (e.g., polyvinylamine), esters (e.g., polycaprolactone, poly(vinyl acetate)), imides (e.g., poly(2-methyl-2-oxazoline)), and copolymers of the foregoing.

Co-binder Optionally, in addition to the polysiloxane-based binder, a co-binder may be present in the coating composition of the present invention. Preferably, the co-binder comprises a curing reactive group capable of reacting with the polysiloxane-based binder in a curing reaction. Representative examples of such co-binders include silicone resins, silicone-epoxy resins, silicone-polyester resins, polyurethane-based binders, polyol-based binders such as acrylic-polyol binders, polyester-based binders, and acrylic-based binders.

Pigments The coating composition of the present invention preferably comprises one or more pigments. The pigments may be inorganic pigments, organic pigments or mixtures thereof. Inorganic pigments are preferred. The pigments may be surface treated.

Representative examples of pigments include black iron oxide, red iron oxide, yellow iron oxide, titanium dioxide, zinc oxide, carbon black, graphite, red molybdate, yellow molybdate, zinc sulfide, antimony oxide, sodium aluminum sulfosilicate, quinacridone, phthalocyanine blue, phthalocyanine green, indanthrone blue, aluminum cobalt oxide, carbazole dioxazine, isoindoline orange, bis-acetoacetoacetotridiol, benzimidazolone, quinaphthrone yellow, isoindoline yellow, tetrachloroisoindolinone, and quinophthalone yellow, metal flake materials (e.g., aluminum flakes). Preferred pigments are black iron oxide, red iron oxide, yellow iron oxide, phthalocyanine blue, and titanium dioxide. In a preferred embodiment, the titanium dioxide is surface treated with a silicone compound, a zirconium compound, or a zinc compound.

The amount of pigment present in the coating composition of the present invention is preferably from 0 to 25% by weight, more preferably from 0.5 to 15% by weight, based on the total dry weight of the coating composition.

Solvent The inventive release coating composition preferably comprises a solvent. Solvents suitable for use in the inventive composition are commercially available.

Examples of suitable organic solvents and diluents are aromatic hydrocarbons such as xylene, toluene, mesitylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, cyclopentanone, cyclohexanone; esters such as butyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, ethylene glycol methyl ether acetate, propylene glycol methyl ether acetate; ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, dioxane, tetrahydrofuran; alcohols such as n-butanol, isobutanol, benzyl alcohol; ether alcohols such as butoxyethanol, 1-methoxy-2-propanol; aliphatic hydrocarbons such as white spirit; and, optionally, mixtures of two or more solvents and diluents.

It is preferred that the amount of solvent present in the inventive release coating composition be as low as possible, as this minimizes the VOC content. Preferably, the solvent is present in the inventive composition in an amount of 0-35% by weight, more preferably 1-30% by weight, based on the total weight of the composition. One skilled in the art will appreciate that the solvent content will vary depending on other ingredients present.

Fillers The coating compositions of the present invention optionally include a filler.

Examples of fillers that can be used in the coating composition according to the invention are zinc oxide, barium sulfate, calcium sulfate, calcium carbonate, fumed silica, silicas or silicates including bentonite and other clays (such as talc, feldspar, kaolin, and nepheline syaenite), and solid silicone resins, which are generally condensed branched polysiloxanes. Some fillers, such as fumed silica, may have a thickening effect on the coating composition.

A preferred filler is a fumed silica filler. The fumed silica filler may have an untreated surface or a hydrophobically modified surface. Preferably, the fumed silica filler has a hydrophobically modified surface. Examples of commercially available fumed silica fillers are TS-610, TS-530, EH-5, H-5, and M-5 from Cabot, and Aerosil® R972, Aerosil® R974, Aerosil® R976, Aerosil® R104, Aerosil® R202, Aerosil® R208, Aerosil® R805, Aerosil® R812, Aerosil® 816, Aerosil® R7200, Aerosil® R8200, Aerosil® R9200, and Aerosil® R711 from Evonik.

The amount of filler present in the coating composition of the present invention is preferably from 0 to 25% by weight, more preferably from 0.1 to 10% by weight, and even more preferably from 0.15 to 5% by weight, based on the total dry weight of the coating composition.

Additives The coating composition of the present invention optionally comprises one or more additives. Examples of additives that may be present in the coating composition of the present invention include reinforcing agents, thixotropic agents, thickening agents, anti-settling agents, dehydrating agents, dispersing agents, wetting agents, surfactants, binders, plasticizers, and dyes.
Examples of thixotropic agents, thickeners and anti-settling agents are silicas such as fumed silica, organomodified clays, amide waxes, polyamide waxes, amide derivatives, polyethylene waxes, oxidized polyethylene waxes, hydrogenated castor oil waxes and mixtures thereof. Preferably, the thixotropic agents, thickeners and anti-settling agents are each present in the composition of the present invention in an amount of 0 to 10 wt.-%, more preferably 0.1 to 6 wt.-%, even more preferably 0.1 to 2.0 wt.-%, based on the total dry weight of the composition.

Dehydrating agents and drying agents that may be used in the deposit release coating composition include organic and inorganic compounds. Dehydrating agents can be hygroscopic materials that absorb water or bind water as water of crystallization, often referred to as desiccants. Examples of desiccants include calcium sulfate hemihydrate, anhydrous calcium sulfate, anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous zinc sulfate, molecular sieves, and zeolites. Dehydrating agents can be compounds that chemically react with water. Dehydrating agents that react with water include orthoesters such as trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, triisopropyl orthoformate, tributyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, tributyl orthoacetate, and triethyl orthopropionate; ketals; acetals; enol ethers; orthoborates such as trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate, and tri-tert-butyl borate; and organosilanes such as trimethoxymethylsilane, vinyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, and ethyl polysilicate.

Preferably, the dehydrating agent is present in the composition of the present invention in an amount of 0-5 wt.%, more preferably 0.5-2.5 wt.%, even more preferably 1.0-2.0 wt.%, based on the total dry weight of the composition.

Compositions and Coatings The present invention also relates to a process for preparing the compositions described hereinbefore, by mixing the ingredients present in the composition. Any conventional manufacturing process can be used.

The compositions described herein may be prepared in a concentration suitable for use in, for example, spray painting, in which case the composition is itself a paint. Alternatively, the composition may be a concentrate for preparing a paint, in which case additional solvent and optionally other ingredients are added to the compositions described herein to form the paint. Preferred solvents are as described above for the compositions.

After mixing, and optionally after the addition of a solvent, the adhesion release coating composition or paint is preferably filled into a container. Suitable containers include cans, drums and tanks.

The adhesion release coating composition may be supplied as a one-part, two-part or three-part composition. Preferably, the composition is supplied as a two-part or three-part composition, and even more preferably as a three-part composition.

When supplied as a one-part product, the composition is preferably supplied in a ready-to-mix or ready-to-use form. Optionally, one-part products can be thinned with a solvent prior to application.

If supplied as a two-part formulation, the first container preferably contains the polysiloxane binder, the non-ionic hydrophilically modified polysiloxane, and the stain repellent, and the second container preferably contains the crosslinker/curing agent and/or catalyst. Optionally, instructions for mixing the contents of the containers may be provided.

When supplied as a three-part formulation, the first container preferably contains the polysiloxane binder, the soil release agent and the non-ionic hydrophilically modified polysiloxane, the second container preferably contains the crosslinker/hardener, and the third container preferably contains the catalyst. Optionally, instructions for mixing the contents of the containers may be provided.

In certain embodiments, the present invention provides a kit for preparing a deposit stripping composition as defined herein.

The release coating compositions and paints of the present invention preferably have a solids content of 50 to 99% by weight, more preferably 60 to 99% by weight, and even more preferably 65 to 99% by weight.
Preferably, the release coating compositions and paints of the present invention have a volatile organic compound (VOC) content of 50 to 400 g/L, preferably 50 to 350 g/L, for example 50 to 300 g/L. The VOC content can be calculated (ASTM D5201-05A) or measured (US EPA Method 24 or ISO 11890-1).

Preferably, the adhesion release coating composition and paint of the present invention have a viscosity of 700 to 1100 mPa at a shear rate of 100/s.

The coating composition of the present invention may be applied to any pretreated coating layer designed for polysiloxane-based fouling release coating. Examples of such coating layers are epoxy anticorrosive layers and silicone-containing tie layers designed to ensure adhesion between the substrate and the final polysiloxane-based fouling release layer. An example of such a tie layer is described in WO 2013/107827. Optionally, the tie layer may include an antifouling agent.

The coating composition of the present invention can also be applied to a substrate containing an old antifouling coating layer or an adhesion release layer. Before applying the coating composition of the present invention to such an old layer, the old layer is washed with high-pressure water to remove dirt.

The coating composition according to the invention can be applied in one layer or two or more layers. Preferably, the coating composition according to the invention is applied in one layer.

The dry thickness of each coating layer of the coating composition of the present invention is preferably 50 to 500 μm, more preferably 100 to 400 μm, and most preferably 150 to 300 μm.

The fouling release coating compositions and paints of the present invention can be applied to all or part of the surface of any article exposed to marine fouling. The surface may be permanently submerged or may be intermittently submerged (e.g., due to tidal movements, different cargo weights, or wave swell). The surface of the article is typically the hull of a ship or the surface of a fixed marine object such as an oil platform or buoy. Application of the coating compositions and paints can be accomplished by any convenient means, for example, by painting (e.g., with a brush or roller) or, more preferably, by spraying the coating onto the article. Typically, the surface must be isolated from seawater to allow coating. Application of the coating can be accomplished as conventionally known in the art. After application of the coating, the coating is preferably dried and/or cured.

Application The fouling release coating of the present invention is typically applied to the surface of marine structures, preferably the part of the marine structure that is submerged in use.Typical marine structures include ships (including but not limited to boats, yachts, motorboats, motor boats, marine liners, tugboats, tankers, container ships and other cargo ships, submarines, and all types of naval vessels), pipes, onshore and offshore machinery, structures, and objects of all types, such as piers, pilings, bridge substructures, hydraulic equipment and structures, underwater oil well structures, nets and other aquaculture equipment, and buoys.The surface of the substrate may be a "natural" surface (e.g., a steel surface).

[Example]
Quantitative methods
Determination of polymer average molecular weight distribution
The polymers were characterized by gel permeation chromatography (GPC) measurements. Molecular weight distributions (MWD) were determined using a Malvern Omnisec Resolve and Reveal system equipped with two PLgel 5 μm Mixed-D columns in series from Agilent. The columns were calibrated by conventional calibration using narrow polystyrene standards. The analytical conditions were as shown in Table 1 below.

Samples were prepared by dissolving an amount of nonionic hydrophilically modified polysiloxane equivalent to 25 mg of dry polymer in 5 ml of THF. The samples were kept at room temperature for a minimum of 3 hours and then sampled for GPC measurement. Before analysis, the samples were filtered through a 0.45 μm nylon filter. The weight average molecular weight (Mw) and number average molecular weight (Mn) are recorded.

Measurement of Viscosity of Nonionic Hydrophilically Modified Polysiloxanes The viscosity of the nonionic hydrophilically modified polysiloxanes was measured using a Brookfield viscometer and spindle. Viscosity was measured at 25°C using a Brookfield LVT viscometer and corresponding LV spindle. The spindle was selected appropriately for the specification range of the nonionic hydrophilically modified polysiloxane in accordance with BROOKFIELD DIAL VISCOMETER Operating Instructions, Manual No. M/85-150-P700, Brookfield Engineering Laboratories, Inc.

Measurement of Viscosity of Paint Formulations The viscosity of the paint formulations (inventive examples and comparative examples) was measured by cone plate at 23° C. Cone diameter 40 mm, cone angle 4°. The shear rate was increased from 0.01/s to 100/s to obtain the shear rate dependent viscosity of the samples.

Preparation of Coating Compositions First, the coating compositions were prepared by mixing the components of part (A) shown in Tables 5 and 6 below using a high-speed dissolver equipped with an impeller disk. The non-ionic hydrophilically modified polysiloxane was added to the coating composition after the grinding stage. The components of part (B) were mixed with the components of part (A) immediately before applying the coating.

Antifouling performance testing in Singapore
PVC panels were coated using an airless spray under the specified conditions with a first coat of Jotun Jotacote Universal N10 primer and a second coat of Jotun SeaQuest Tiecoat. The inventive and comparative coating compositions were applied to PVC panels pre-coated with primer and tie coat using a film applicator with a clearance of 300 μm.

The panels were used in static testing on a floating platform in Singapore, where the panels were submerged 0.3 to 1.3 m below sea level. The panels were visually rated using the scale shown in Table 2 below.

Coating Adhesion Determination Coating adhesion was determined according to ASTM D6677: 18. A rating of 5 or greater was considered acceptable ("OK" in Tables 5 and 6).

Determination of Coating Uniformity The coating uniformity was determined by visual observation according to Table 3.

Nonionic hydrophilically modified polysiloxanes having the properties listed in Table 4 are commercially available and readily available from commercial suppliers.

The coating compositions and antifouling performance of the examples of the present invention and comparative examples are shown in the table below.

With respect to the above example, the following observations can be made.
Comparative Example 2 shows that the addition of copper pyrithione to a coating containing polyether modified polysiloxane increases the viscosity of the coating compared to Comparative Example 1. The increase in viscosity can have a negative effect on application properties and surface roughness. Furthermore, 5 wt. % of oil is not enough to reduce the viscosity increase caused by the addition of copper pyrithione.

-Examples 1 and 2 of the present invention illustrate coating compositions containing copper pyrithione and polyether-modified polysiloxane in amounts of 15-25 wt% oil have good film uniformity and good adhesion while maintaining low VOC. Furthermore, the viscosity increase seen in Comparative Example 2 is offset by the higher oil amount. Antifouling performance is also improved compared to Comparative Example 2 containing 5 wt% polyether-modified polysiloxane.

Comparative Example 2 shows that 5% by weight of oil is insufficient to achieve satisfactory antifouling performance.

Comparative examples 3 and 4 show that dilution with a solvent can reduce the viscosity of a copper pyrithione-containing coating to its original level, but at the expense of increased VOCs, which have adverse effects in terms of health and environmental concerns.

Comparative Example 5 shows that further increasing the oil to 35% by weight (dry weight basis) further reduces VOCs and viscosity, but at the expense of coating uniformity and antifouling performance.

-Inventive Examples 3-6 show that there are several possible polyether modified polysiloxane oils that exhibit good antifouling performance while maintaining good film uniformity and adhesion at oil levels as high as 16 wt% (dry weight basis). Lower viscosity oils provide a greater reduction in the final viscosity of the coating.

Comparative Examples 6 and 7 show that oils with HLB levels above 12 have a detrimental effect on coating uniformity and adhesion at oil concentrations of 16% and 25% by weight (dry weight basis).

Comparative Examples 8-10 show that oils with number average molecular weights above 18,000 give good film uniformity and good adhesion at oil concentrations up to 34 wt. % (dry weight basis), but poor antifouling performance. This is probably because too high a molecular weight limits the movement of the oil through the film. If the viscosity of the oil is too high, more oil is also needed to reduce the viscosity of the paint formulation.

In summary, it has been found that by selecting non-ionic hydrophilically modified polysiloxanes with specific parameters (amount, molecular weight and HLB), it is possible to obtain a fouling release formulation containing a biocide such as copper pyrithione, with low VOC, good application properties, good film uniformity and adhesion, and improved antifouling properties.

Claims (21)

a) a curable polysiloxane-based binder comprising at least 50% by weight of polysiloxane moieties;
b) a stain repellent;
c) 10 to 30% by dry weight,
i) a hydrophilic-lipophilic balance (HLB) of 1 to 12, and
ii) Mn between 500 and 18,000 g/mol
and a non-ionic hydrophilically modified polysiloxane having the formula: a) a curable polysiloxane-based binder comprising at least 50% by weight of polysiloxane moieties;
b) a stain repellent;
c) 10 to 30% by dry weight,
i) a hydrophilic-lipophilic balance (HLB) of 1 to 12, and
ii) Mw between 1,000 and 50,000 g/mol
and a non-ionic hydrophilically modified polysiloxane having the formula: The adhesion release coating composition according to claim 1 or 2, comprising 30 to 95% by weight of a polysiloxane-based binder, based on the total dry weight of the composition. The adhesion release coating composition according to any one of claims 1 to 3, wherein the antifouling agent is present in an amount of 1 to 15% by weight, on a dry weight basis, based on the total dry weight of the composition. The adhesion release coating composition according to any one of claims 1 to 4, wherein the nonionic hydrophilically modified polysiloxane is present in an amount of 11 to 29% by weight (dry weight basis) based on the total dry weight of the composition. The adhesion release coating composition according to any one of claims 1 to 5, wherein the antifouling agent is zinc pyrithione or copper pyrithione. The adhesion release coating composition according to any one of claims 1 to 6, wherein the nonionic hydrophilically modified polysiloxane has a number average molecular weight (Mn) in the range of 500 to 18,000 g/mol. The adhesion release coating composition according to any one of claims 1 to 7, wherein the nonionic hydrophilically modified polysiloxane has a viscosity in the range of 20 to 4,000 mPa-s. The adhesion release coating composition according to any one of claims 1 to 8, wherein the nonionic hydrophilically modified polysiloxane has a weight average molecular weight (Mw) of 2,000 to 45,000 g/mol. The adhesion release coating composition according to any one of claims 1 to 9, wherein the nonionic hydrophilically modified polysiloxane has an HLB (hydrophilic-lipophilic balance) in the range of 1.0 to 10. The polysiloxane binder is represented by the following formula (D1):

(D1)
[Wherein,
each ^R1 is independently selected from a hydroxyl group, a _C1-6 -alkoxy group, a _C1-6 -hydroxyl group, a _C1-6 -epoxy-containing group, a _C1-6 amine group, or O-Si( ^R5 ) _3-z ( ^R6 ) _z ;
each ^R2 is independently selected from _C1-10 alkyl, _C6-10 aryl, _C7-10 alkylaryl, or _C1-6 alkyl substituted with poly(alkylene oxide) and/or groups described as ^R1 ;
each ^R3 and ^R4 is independently selected from _C1-10 alkyl, _C6-10 aryl, _C7-10 alkylaryl, or _C1-6 alkyl substituted with poly(alkylene oxide);
each ^R5 is independently a _C1-6 alkoxy group, an acetoxy group, an enoxy group, or a ketoxy group ;
each ^R6 is independently selected from an unsubstituted _C1-6 alkyl group or a substituted _C1-6 alkyl group;
z is 0 or an integer from 1 to 2;
x is an integer equal to or greater than 2;
y is an integer equal to or greater than 2.
The release coating composition according to any one of claims 1 to 10. The release coating composition of any one of claims 1 to 11, further comprising at least one of a filler, a pigment, a solvent, an additive, a curing agent, and a catalyst. A paint comprising the deposit release coating composition of any one of claims 1 to 12 and at least one of a filler, a pigment, a solvent, an additive, a curing agent and a catalyst . The adhesion release coating composition according to any one of claims 1 to 12, wherein the nonionic hydrophilic modified polysiloxane is a polyether modified polysiloxane. 13. The adhesion release coating composition according to claim 1, wherein the nonionic hydrophilically modified polysiloxane is non-curable in the curing reaction of the binder at 0 to 40°C. a) a curable polysiloxane-based binder comprising at least 50% by weight of polysiloxane moieties;
b) a stain repellent;
c) 10 to 30% by dry weight,
i) a relative weight of the hydrophilic portion in the range of 5 to 60% by weight, and
ii) Mn between 500 and 18,000 g/mol
and a non-ionic hydrophilically modified polysiloxane having the formula: a) a curable polysiloxane-based binder comprising at least 50% by weight of polysiloxane moieties;
b) a stain repellent;
c) 10 to 30% by dry weight,
i) a relative weight of the hydrophilic portion in the range of 5 to 60% by weight, and
ii) Mw between 1,000 and 50,000 g/mol
and a non-ionic hydrophilically modified polysiloxane having the formula: A marine structure comprising, on at least a portion of its outer surface, a fouling release coating composition according to any one of claims 1 to 12 and 14 to 17. A method for preparing an adhesion release coating composition according to any one of claims 1 to 12, 14 and 15 , comprising the steps of:
a) a curable polysiloxane-based binder comprising at least 50% by weight of polysiloxane moieties;
b) a stain repellent;
c) 10 to 30% by dry weight,
i) HLB from 1 to 12, and
ii) Mn of 500 to 18,000 g/mol and/or Mw of 1,000 to 50,000 g/mol
and a non-ionic hydrophilic modified polysiloxane having the formula:
The method typically includes the step of mixing in at least one solvent. 18. A method for preparing an adhesion release coating composition according to claim 16 or 17, comprising the steps of :
a) a curable polysiloxane-based binder comprising at least 50% by weight of polysiloxane moieties;
b) a stain repellent;
c) 10 to 30% by dry weight,
i) the relative weight of the hydrophilic portion in the range of 5 to 60% by weight, and
ii) Mn of 500 to 18,000 g/mol and/or Mw of 1,000 to 50,000 g/mol
and a non-ionic hydrophilic modified polysiloxane having the formula:
The method typically includes the step of mixing in at least one solvent. A kit for preparing the adhesion release coating composition according to any one of claims 1 to 12 and 14 to 17, comprising:
(i) a first container containing a curable polysiloxane-based binder, a stain repellent, and/or a non-ionic hydrophilically modified polysiloxane;
(ii) a second container containing a crosslinker and/or curing agent, and optionally a catalyst;
(iii) optionally, a third vessel containing a catalyst;
(iv) optionally, instructions for combining the contents of said containers.